Synergistic insecticidal compositions



SYNERGISTIC INSECTICIDAL CGMIOSITIONS Howard A. Jones and John A. Garman, Baltimore, Md,

and Berton 'C. Dickinson, Lyndonville, N.Y., assignors to Food Machinery and Chemical Corporation, New

York, N.Y., a corporation of Delaware No Drawing. Filed Oct; 23, 1958, Ser. No. 769,078

2 Claims. (Cl. 167-22) This invention relates broadly to insecticidal compositions, and more particularly to insecticidal compositions containing an organic carbamate acid derivative and 0,0-dimethyl-S-(1,2 dicarbethoxyethyl) dithiophosphate, hereinafter referred to as Malathion. More particularly, this invention relates to synergistic insecticidal compositions of these compounds wherein the insecticidal eflectiveness of each component is enhanced by the presence of the other to produce an unexpected combined efiect.

When two or more substances in combination show an unexpectedly high activity, as for instance, insecticidal activity, the resulting phenomenon is called synergism. The mechanism of synergism is by no means understood. It is, in fact, quite probable that it diiiers with dififerent synergistic combinations. The term synergism can be defined, however; as a cooperative action which is encountered in combinations of two or more biologically active components in which the combined activity of the two components exceeds the sum of the activities of the components when used alone. The insecticidal activity of the mixed components cannot be predicted from known values of the individual components, but is unpredictable and depends on the individual activity of neither.

It is an object of this invention to provide insecticidal compositions of enhanced killing power. Another object of this invention is to produce novel compositions containing compounds capable of synergizing the knockdown and killing properties of individual toxicants. A further object of this invention is to provide compositions including'a relatively toxic phosphorus containing insecticide in which superior insecticidal activity is obtained because of the synergistic eifects, but in which the ultimate toxicity to warm-blooded animals is greatly reduced because of the lower concentrations of the phosphorous compounds required when used in combination with the relatively less toxic carbamates. Other objects and advantages of the invention will become apparent from the description of the invention set forth below.

According to this invention there are provided synergistic insecticidal compositions comprising 0,0-dimethyl S-(1,'2 dicarbethoxyethyl) dithiophosphate, hereinafter called Malathion, and an organic carbamate ester of the following general formula wherein R is selected from the group consisting of ethyl and isopropyl and R is selected from the group consisting of tert-butyl, sec-butyl and 3-trifiuoromethylphenyl. These carbamates may be prepared as described in copending application Serial No. 812,113, filed May 11, 1959.

The synergistic insecticidal compositions of this invention may be used on a wide variety of insect and mite species, but are particularly effective against such insects as the two-spotted spider mite. The combinations are highly efiective and economical to use for such large-scale insecticidal requirements as the control of truck crop, forage crop and orchard insects.

The synergistic compositions of this invention can be formulated as aqueous emulsions, as dry or wettable ice powders, as solutions or in any other suitable vehicle. The insecticidal compositions can be utilized as sprays, as dusts, as aerosol mixtures, insecticidal coating compositions, and as residues. In general, they can be applied by methods commonly used for control of eradication of insects, mites and the like. Thus these insecticidal compositions can be formulated with solvents, diluents and carrier media, adhesives, spreading, wetting and emulsifying agents and other ingredients.

The relative proportions of the active ingredients as well as inert carriers, solvents, dispersants and the like may vary within wide limits.

Thus the relative proportion (ratio) of the Malathion to the carbamate ester can range from 20 parts of the former per 1 part of the latter to 1 part of the former per 40 parts of the latter and preferably about 1 part of the former to about 2 parts of the latter.

7 The quantities of the component toxicants in the final insecticidal compositions can range from 0.01% to 25.00% for the Malathion and from 0.05% to 50.00% for the carbamate, and preferably from 0.10% to 10.00% for the Malathion and from 0.10% to 25.00% for the carbamate.

The procedures of the testing methods are described below. The details of the test experiments including the type of formulation and mode of application or dosing, and the species of insects which served as test subjects are given in the examples.

Insects used in the testing including the house fly (Musca domestica L.), Mexican bean beetle (Epilachtm varivestis Muls.), pea aphid (Macrosiphum pisi [Kltb.] two-spotted spider mite (Tetranychus bimacu'latus Harvey), harlequin bug (Mu'rgantia Histrionica [Hahn]) and squash bug (Anasa tristis).

The test methods used are described as follows:

DUST TOWER METHOD The dusting apparatus consists of a vertical glass cylinder, '34 inches high and 8.5 inches in diameter, into which the appropriate dust sample is discharged through a small hole in the center of the cover, by means of a small laboratory duster operating at an air pressure of 40 p.s.i.g. The duster assembly comprises a 10 ml. beaker, into which the weighed sample is placed, and fitted with a rubber stopper through which pass the air inlet and dust outlet tubes, both of which are made of inch diameter copper tubing. At the outer end of the air inlet tube is a trigger valve that serves as a control for dispensing the dust. The inner end of this tube reaches nearly to the bottom of the beaker. The end of it is sealed but, along the sides, seven 0.032 inch holes are drilled at irregular intervals which serve as air inlets. Such an arrangement causes pronounced turbulence of the dust and thus insures exhausting the complete sample from the beaker. The dust outlet tube forms an arch from the top of the beaker to the top of the glass dusting tower. After discharge of the sample into the tower, there is allowed a two-minute settling time before removal of foliage or insects being treated. A weighed metal plate is placed in the tower each time a test is made, and by weighing the amount of dust deposited on it, it is then possible to calculate the amount applied per acre.

Because of day-to-day variations in the results obtained by this test method, comparisons among the individual components and their combinations were made simultaneously in order to minimize this source of variation.

Slight modifications in this test employed for specific insect species are as noted below.

Two-spotted spider mite.-ln tests on two-spotted mites, the mites were confined to the upper surfaces of potted bean plants by a Tange1footfring. The bean plants O-dimethyl S-(1,2-dicarbethoxyethy1)dithiophosphate and were placed in the glass tower and the mites directisopropyl N-(3-trifluoromethylphenyl)-earbarnate, said dusted. Mortality readings were taken in 24 hours. components being present in the ratio of about 2 parts of Only adult mites were used in determining mortality said carbamate ester to about 1 part of said dithiphos-.

counts; f 7 i 5 phate.

r r H 'V i In NGOOR V r I H. H

Oarbamete 7 Phosphate a a Rate V 7 Mortal! Dust ,Dust (Lb'sJ Test Method Test Subleut (Percent -'IR|; R 00110. Name Gone. 11.) a a (Per- (Pen cent) cent) V time. Ethyl.r 7] 9.1 Dust Tower--. Two'spotted Spider Mimi.-- o Malathion 0.6 8.0 e 69 Do do 1 do 0.5 6.7 n 99 seo.-.Buty1. Isopropyl 1 22.8 fin 2 Malethlon 0.5 20.3 fin fin 61 .D .-do 1 do---.- 0.5 17.6 an dn s2 Ethy1 2-.Ethy1hexyl. 1 26.8 in Mexican BeanIBeetle 5 Malathion 0.5 19.8 5 D0,.-. .r do 1 .-do.. 0.5 20.6 -i 65 0. 010-1 Isopropyl.. 1 20.4 do do 0 w Malathion 0. 5 16.9 .---.do 21 Do "do 1 do 0.6 16.6 do r-.' fin 83 3-Trifluorodo 1 19.5 ...,...do Two-spotted Spider Mlte..... 0

methyl- V .phenyl. 1 7 I.

I Melathion -o.5 20.3 fin a: DQ .do 1 d0. 0.5 i4'8 fl do 84 I I The results of the data summarized in Table, 1 demon- I References Cited ill 121181 file 'of this patent I strate the marked synergism of the insecticidal composi- UNITEDVATES N tions of this invention. 7 3 3 k .A .1 This application is a division of copending application 35 2,50 1 g Serial No. 49 6,596, fi1ed March 24, 1955, now aban- 2,679,598 '-M F 5- doned, which is a continuation-in-part of Serial No. 427,- r r OTHER t V 374, E 3, 1.954,

King: USDAHandbook No. 69, May 1954, pp. 1051 What is claimed is: 108. 1; Synergistic insecticidal. Q 1 fi9 wmprisins Chem. Age, v01. 63, No. 1631 1950 p. 540. v. 0-d1methy1SAhl-dwarbethoxyethyl)dlthwrhosphate and Sharp: Agr. News Letter, January-February 1952, pp. isopropyl N-sec.-buty1'carbamate; said components being 1-3, a I J j present in the ratio of about 2 parts ofsaid carbamate Roark: USDA Bull, 13-344 (May. 1935), .& ester to about 1 part of said dithiophosphate. 45 Freer: Chem. of the Pesticides, 2nd ed., January 2. Synergistic insecticidal compositions comprising 0, pp. 73-91. v r I V 

1. SYNERGISTIC INSECTIDAL COMPOSITIONS COMPRISING O, O-DIMETHYL S-(1,2-DICARBETHOXYETHYL) DITHIOPHOSPHATE AND ISOPROPYL N-SEC.-BUTYL CARBAMATE, SAID COMPONENTS BEING PRESENT IN THE RATIO OF ABOUT 2 PARTS OF SAID CARBAMATE ESTER TO ABOUT 1 PART OF SAID DITHIOPHOSPHATE. 